阅读说明：本技术 一种处理偏二甲肼废水的方法 (A method of processing uns-dimethylhydrazine waste water ) 是由 贾瑛 吕晓猛 许国根 王坤 于 2019-08-29 设计创作，主要内容包括：本发明公开了一种处理偏二甲肼废水的方法,该方法包括：过二硫酸盐在催化量的碳酸根离子和/或碳酸氢根离子的催化下对偏二甲肼废水进行氧化降解处理,氧化降解处理时偏二甲肼废水的温度在40℃以上。与现有技术相比,本发明方法对偏二甲肼具有良好的去除和矿化效果,所用的药剂易于获取、储存,使用成本低,且不会产生二次污染,更为环保,可对发动机试车、火箭点火时产生的高温偏二甲肼废水直接进行原位处理。(The invention discloses a kind of methods for handling uns-dimethylhydrazine waste water, this method comprises: peroxydisulfate carries out oxidative degradation processing to uns-dimethylhydrazine waste water under the catalysis of the carbanion and/or bicarbonate ion of catalytic amount, the temperature of uns-dimethylhydrazine waste water is at 40 DEG C or more when oxidative degradation is handled.Compared with prior art, the method of the present invention has good removal and remineralization efficacy to uns-dimethylhydrazine, medicament used is easily obtained, stores, use cost is low, and secondary pollution will not be generated, more environmentally friendly, the high temperature uns-dimethylhydrazine waste water generated when can be to engine test, rocket firing directly carries out in-situ treatment.)

1. a kind of method for handling uns-dimethylhydrazine waste water, comprising: carbanion and/or carbonic acid of the peroxydisulfate in catalytic amount Oxidative degradation processing is carried out to uns-dimethylhydrazine waste water under the catalysis of hydrogen radical ion, the temperature of uns-dimethylhydrazine waste water when oxidative degradation is handled Degree is at 40 DEG C or more.

2. according to the method described in claim 1, it is characterized by: the mole dosage of the peroxydisulfate and uns-dimethylhydrazine ratio For 0.5:1~30:1.

3. according to the method described in claim 2, it is characterized by: the mole dosage of the peroxydisulfate and uns-dimethylhydrazine ratio For 5:1~15:1, it is highly preferred that the mole dosage of the peroxydisulfate and uns-dimethylhydrazine ratio is 10:1~12:1.

4. any method according to claim 1~3, it is characterised in that: the peroxydisulfate be selected from sodium persulfate, Potassium persulfate, ammonium peroxydisulfate.

5. according to the method described in claim 1, it is characterized by: the carbanion and/or bicarbonate ion and institute The mole dosage ratio for stating peroxydisulfate is 10:1~1:20.

6. according to the method described in claim 5, it is characterized by: the carbanion and/or bicarbonate ion and institute The mole dosage ratio for stating peroxydisulfate is 1:1~1:10, it is highly preferred that the carbanion and/or bicarbonate ion Mole dosage ratio with the peroxydisulfate is 1:2~1:4.

7. according to claim 1, method described in 5 or 6, it is characterised in that: the carbanion and/or bicarbonate ion It is provided by water soluble carbonate and/or bicarbonate.

8. according to the method described in claim 7, it is characterized by: the carbonate be selected from sodium carbonate, potassium carbonate, ammonium carbonate, The bicarbonate is selected from sodium bicarbonate, saleratus, ammonium hydrogen carbonate.

9. any method according to claim 1~8, it is characterised in that: when oxidative degradation is handled, uns-dimethylhydrazine waste water Temperature is 50~100 DEG C, it is highly preferred that the temperature of uns-dimethylhydrazine waste water is 60~80 DEG C.

10. the purposes of water soluble carbonate and/or bicarbonate, which is characterized in that the water soluble carbonate and/or bicarbonate Salt is as catalyst for being catalyzed peroxydisulfate oxidative degradation uns-dimethylhydrazine.

Technical field

The invention belongs to field of waste water treatment, and in particular to a method of processing uns-dimethylhydrazine waste water, especially with The method that oxidizing process carries out degradation treatment to uns-dimethylhydrazine in waste water.

Background technique

Uns-dimethylhydrazine, i.e. 1,1- dimethyl hydrazine are the main bodys of the emission tests such as guided missile, satellite, airship and carrier rocket Fuel has the advantages of high specific impulse value, good thermal stability, but it is with stronger toxicity, has carcinogenic, mutagenesis etc. to human body Harm.The waste water that generates can cause to seriously endanger to staff and ecological environment during production, transport, using etc..

The processing method of existing uns-dimethylhydrazine waste water has physical treatment process (absorption method, ion-exchange, permeable membrane^[1]), it is raw Object edman degradation Edman^[2], method of chemical treatment etc., wherein although physical treatment process and biodegrade and chemical treatment are without chemical agent tool Have the advantages that simple and practical, but the regeneration of adsorbent material, ion exchange material is easy to produce secondary pollution.Biological degradation method has Green, the advantage of environmental protection, but the existence of microorganism and breeding are more sensitive to temperature and pH etc., just easy quilt after temperature reaches 55 DEG C It kills, needing first to carry out cooling processing for the high temperature uns-dimethylhydrazine waste water generated when engine test, rocket firing could fit With.

The chemical treatment method of current common uns-dimethylhydrazine waste water is mainly chemical oxidization method, such as Fenton method^[3-4], light urges Change oxidizing process^[5-8], super (close) critical water oxidation^[9]Deng and chemical reduction method^[10].Fenton method is due to that need to add Fe²⁺, meeting Chroma in waste water is caused to increase, and Fe²⁺It is also easy to produce molysite deposition (Fe (OH)₃), it is not easily settled.Photocatalytic oxidation generally requires purple Outer light is as energy, and semi-conductor types (such as TiO such as metal oxide or sulfide for needing to be added higher cost₂, ZnO etc.) Solid catalyst, there are equipment and energy cost are higher, the difficult problem of catalyst recycling.Super (close) critical oxidation rule pair More stringent requirements are proposed for the super pressure-high temperature high-voltage performance of equipment.

The common oxidising agent of oxidative degradation uns-dimethylhydrazine waste water has ozone, hydrogen peroxide, Cl₂, hypochlorite etc..Ozone needs Ozone generating-device is provided, equipment investment, operation expense are high.Dioxygen water unstable is not easy to deposit long, and is liquid, no Just it transports and stores.Cl₂, hypochlorite degradation uns-dimethylhydrazine process then exist be also easy to produce nitroso compound, formaldehyde, The problem of secondary pollutions such as inclined hydrazone.These different oxidising agents can be used in combination, to overcome single oxidising agent not Foot^[11]。

Compared with common hydrogen peroxide, the peroxydisulfate for belonging to peroxide is then comparatively stable, and is solid, Easily stored and transport.Chinese patent literature CN109179622A is disclosed in a kind of oxidizing agent composition and processing trade effluent The method of hydrazine hydrate, and specifically disclose a kind of Fe (III) complex and sodium persulfate (potassium) group including 2,2 '-bipyridyls At oxidizing agent composition, the oxidizing agent composition is good to hydrazine hydrate under the catalysis of nickel chloride, copper chloride and zinc sulfate etc. Degradation effect.The deficiency of the technology is that sodium persulfate needs are used in combination with F (III) complex, so that reagent cost It is higher, and the heavy metal ion such as iron ion, nickel ion, copper ion are easy to produce secondary pollution.

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Summary of the invention

Based on the deficiency of above-mentioned existing chemical oxidation degradation uns-dimethylhydrazine, the object of the present invention is to provide one kind to cross two sulphur Hydrochlorate is the method for oxidizer treatment uns-dimethylhydrazine waste water.

To achieve the above object, the technical solution adopted in the present invention is as follows:

A method of processing uns-dimethylhydrazine waste water, comprising: carbanion and/or carbon of the peroxydisulfate in catalytic amount Oxidative degradation processing is carried out to uns-dimethylhydrazine waste water under the catalysis of sour hydrogen radical ion, uns-dimethylhydrazine waste water when oxidative degradation is handled Temperature is at 40 DEG C or more.

Preferably, the mole dosage of the peroxydisulfate and uns-dimethylhydrazine ratio be 0.5:1~30:1, as 0.5:1,1:1, 2:1、4:1、5:1、8:1、10:1、11:1、12:1、14:1、15:1、16:1、20:1、25:1、30:1。

It is highly preferred that the mole dosage of the peroxydisulfate and uns-dimethylhydrazine ratio is 5:1~15:1, most preferably, institute The mole dosage ratio for stating peroxydisulfate and uns-dimethylhydrazine is 10:1~12:1.

Preferably, the peroxydisulfate is selected from sodium persulfate, potassium persulfate, ammonium peroxydisulfate.

Preferably, the mole dosage ratio of the carbanion and/or bicarbonate ion and the peroxydisulfate is 10:1~1:20, as 10:1,8:1,6:1,4:1,2:1,1:1,1:2,1:3,1:4,1:5,1:6,1:8,1:10,1:12,1:14, 1:17、1:20。

It is highly preferred that the mole dosage ratio of the carbanion and/or bicarbonate ion and the peroxydisulfate For 1:1~1:10.

Most preferably, the mole dosage ratio of the carbanion and/or bicarbonate ion and the peroxydisulfate For 1:2~1:4.

Preferably, the carbanion and/or bicarbonate ion are mentioned by water soluble carbonate and/or bicarbonate For.

Preferably, the carbonate is selected from sodium carbonate, potassium carbonate, ammonium carbonate, and the bicarbonate is selected from sodium bicarbonate, carbon Potassium hydrogen phthalate, ammonium hydrogen carbonate.

Preferably, when oxidative degradation is handled, the temperature of uns-dimethylhydrazine waste water is 50~100 DEG C, it is highly preferred that uns-dimethylhydrazine The temperature of waste water is 60~80 DEG C.

For the pH value of uns-dimethylhydrazine waste water, there is no particular limitation, can be controlled in 3~12, preferably pH value is can be controlled in 5~12, more preferably pH value can be controlled in 7~11, and most preferably, pH value can be controlled in 9~11.

The purposes of water soluble carbonate and/or bicarbonate, it is characterized in that, the water soluble carbonate and/or carbonic acid Hydrogen salt is as catalyst for being catalyzed peroxydisulfate oxidative degradation uns-dimethylhydrazine.

Beneficial effect

1, compared with other anion (such as chloride ion), present inventors have unexpectedly found that carbonic acid (hydrogen) radical ion can significantly improve Oxidative degradation efficiency of the dithionate to uns-dimethylhydrazine.

2, compared with ozone, hydrogen peroxide, medicament used in the method for the present invention is easily obtained, stores, and use cost is low, and not The secondary pollution of heavy metal ion can be generated, it is more environmentally friendly.

3, compared with biological treatment, the high temperature generated when the method for the present invention is without to engine test, rocket firing is inclined Dimethylhydrazine waste water carries out cooling treatment, can directly carry out in-situ oxidation degradation treatment.

4, compared with Fenton method, the method for the present invention increases there is no chroma in waste water and generates the hydroxide for being difficult to settle The problem of iron.

5, compared with photocatalytic oxidation, the method for the present invention is without UV energy device and can save solid catalyst Recycling.

Detailed description of the invention

Fig. 1 is influence of the uns-dimethylhydrazine solution ph to uns-dimethylhydrazine removal rate；

Fig. 2 is influence of the uns-dimethylhydrazine solution temperature to uns-dimethylhydrazine removal rate；

Fig. 3 is influence of the carbanion to uns-dimethylhydrazine removal rate；

Fig. 4 is influence of the carbanion to uns-dimethylhydrazine mineralization rate；

Fig. 5 is the influence that methanol is catalyzed lower sodium persulfate oxidative degradation uns-dimethylhydrazine to carbanion；

Fig. 6 is the degradation reaction mechanism of uns-dimethylhydrazine of the present invention；

Fig. 7 is influence of the chloride ion to uns-dimethylhydrazine removal rate；

Fig. 8 is influence of the sodium persulfate to uns-dimethylhydrazine removal rate.

Specific embodiment

In order to be better understood by technical solution of the present invention, the present invention is done further in detail below by way of preferred embodiment It describes in detail bright.

(1) initial influence of the pH to sodium persulfate oxidative degradation uns-dimethylhydrazine (UDMH)

The UDMH solution (its nature pH is about 9.0) that 100mL initial concentration is 100mg/L is added to 150mL conical flask In, use H₂SO₄PH value of solution is adjusted with NaOH and is placed on constant-temperature table, wait be preheating to 70 DEG C, is added by initial concentration for 20mmol/L Enter sodium persulfate (PS) to start to react, every 10min, takes 0.2mL sample to be put into colorimetric cylinder, be put into ice in colorimetric cylinder in advance Then water carries out UDMH content measuring with spectrophotometry to terminate reaction, calculate UDMH removal rate.

As shown in Figure 1, UDMH degradation rate and removal rate difference are little under the conditions of different initial pH (3~11), in acidity With the removal rate of UDMH is up to 82.5% in 60min under neutrallty condition, and when initial reaction system be alkalinity when, UDMH's goes Except rate gradually rises, when pH value is 11, the removal rate of UDMH reaches 89.5%.

(2) influence of the temperature to sodium persulfate oxidative degradation UDMH

The UDMH solution that 100mL initial concentration is 100mg/L is added in 150mL conical flask, wait be preheating to specified temperature After degree, it is that 20mmol/L addition sodium persulfate starts to react by initial concentration, every 10min, 0.2mL sample is taken to be put into colorimetric Guan Zhong is put into ice water in colorimetric cylinder to terminate reaction in advance, then carries out UDMH content measuring, calculating UDMH with spectrophotometry Removal rate.

As shown in Fig. 2, as the temperature rises, the degradation rate of UDMH is dramatically speeded up.When temperature is 40 DEG C and 50 DEG C, heat It is very limited to the degradation of UDMH to activate sodium persulfate, reacts 1 hour UDMH removal rate less than 5%；When temperature is increased to 80 DEG C when, the removal rate of UDMH reaches 100%.It can be seen that temperature influences significantly, to work as temperature on thermal activation sodium persulfate degradation UDMH When raising, the free radical quantity that thermal activation sodium persulfate generates increases, to accelerate the degradation of UDMH.

(3) promotion of the carbanion to sodium persulfate oxidative degradation UDMH

1, the UDMH solution that 100mL initial concentration is 100mg/L is added in 150mL conical flask, by different initial dense Degree is added quantitative aqueous sodium carbonate and is placed on water-bath constant temperature oscillator, is 20mmol/ by initial concentration wait be preheating to 70 DEG C L is added sodium persulfate and starts to react, and every 10min, takes 0.2mL sample to be put into colorimetric cylinder, is put into ice in colorimetric cylinder in advance Then water carries out UDMH content measuring with spectrophotometry to terminate reaction, calculate UDMH removal rate.Reaction measures after 1 hour System total organic carbon (TOC) calculates UDMH mineralization rate.

Different initial concentration CO₃ ^2-The influence that (5,10,50,100mmol/L) degrade to UDMH is as shown in figure 3, from Fig. 3 Know CO₃ ^2-Presence have very strong facilitation to the degradation of UDMH, and work as CO₃ ^2-Concentration does not occur dropping UDMH when increasing The inhibition situation of solution.When being not added with CO₃ ^2-When, UDMH is 86.7% in 1 hour removal rate, and as addition 5mmol/L CO₃ ^2- When, removal rate of the UDMH in 30min has just reached 94.5%.It can be seen that CO₃ ^2-There is very strong facilitation to UDMH degradation.

As shown in figure 4, UDMH is easy to be converted to many intermediate products in degradation process, being difficult permineralization is CO₂With H₂O.Do not add CO₃ ^2-When, the mineralization rate that UDMH reacts 1 hour only has 7.8%, with CO₃ ^2-The increase of initial concentration, UDMH's Mineralization rate increases rapidly, works as CO₃ ^2-Concentration is 10mmolL^-1When, the mineralization rate highest of UDMH, the TOC removal rate of reaction 1 hour Reach 87.1%, than CO is not added₃ ^2-When mineralization rate improve nearly 10 times, work as CO₃ ^2-The mineralization rate of UDMH is anti-when concentration continues to increase And it reduces.Reason may be to work as CO₃ ^2-Initial concentration is more than 10mmolL^-1When, generate more CO₃ ^·-It can be competed with organic matterReaction rate is reduced, the reduction of UDMH mineralization rate is caused.Therefore, by reality It tests data and obtains and work as CO₃ ^2-Most beneficial for the mineralizing and degrading of UDMH when molar ratio with PS is 1:2.

NO in system₂ ^-、NO₃ ^-、NH₄ ⁺And total nitrogen change over time as shown in table 1 (UDMH initial concentration be 100mgL^-1, CO₃ ^2-Concentration is 10mmolL^-1, PS concentration is 20mmolL^-1, temperature is 70 DEG C), it there is in initial stage solution few The NO of amount₂ ^-、NO₃ ^-、NH₄ ⁺, it may be possible to due to caused by going bad part during UDMH storage.With the progress of reaction, inorganic nitrogen Overall content constantly increases, and wherein ammonium radical content is higher, and nitrate anion and nitrite anions content are lower, and both rear may be derived from ammonium The oxidation of radical ion generates.The mass concentration of total nitrogen in solution is gradually decreasing, this explanation has part nitrogen with the shape of nitrogen Formula removes.Inorganic nitrogen/total nitrogen ratio with reaction constantly increase, illustrate UDMH gradually Degradation and Transformation be inorganic nitrogen, 40min with It may be because the consumption of free radical isoreactivity ingredient results in reaction rate in reaction system that ratio decrease speed is slack-off afterwards It reduces.Meanwhile with the progress of reaction, the pH value of reaction system is gradually decreased, due to OH^-It is a large amount of consumption and small molecule it is organic The generation of acid causes reaction system pH decline obvious, and pH value can drop to 3.5 or so from original 10.5.

The variation of inorganic nitrogen and total nitrogen in 1 UDMH degradation process of table

2, in order to verify carbanion to the degradation facilitation of UDMH, 1molL is first added into system^-1Methanol (MeOH), sodium persulfate (PS/CO is added₃ ^2-/MeOH)。CO₃ ^2-Addition can change the pH value of solution, so that solution is shown highly basic Property, pH value can rise to 10.5 or so, therefore, in order to exclude the interference that pH value degrades to UDMH, the phosphate for being 10.5 with pH value Buffer substitutes aqueous sodium carbonate and carries out control experiment (PS/pH10.5buffer/MeOH).As a result as shown in Figure 5.Methanol can To capture SO₄ ^·-And OH, reaction rate constant are respectively 1.6 × 10⁷~7.7 × 10⁷L·(mol·s)^-1、1.2×10⁹ ~2.8 × 10⁹L·(mol·s)^-1, and methanol and CO₃ ^·-It hardly reacts, reaction rate constant is less than 2.6 × 10³L· (mol·s)^-1。

As shown in Figure 5, degradation of the UDMH in PS/pH10.5buffer/MeOH is obviously inhibited, and illustrates SO₄ ^·-With OH can be quenched by methanol, to reduce the removal rate of UDMH.CO is added under the conditions of identical pH₃ ^2-The degradation of UDMH can be mentioned Effect is risen, promoting effect may be due to CO₃ ^2-With the SO in MeOH competitive reaction system₄ ^·-And OH, and then generate CO₃ ^·-, CO₃ ^·-The degradation of UDMH is promoted as new active specy.Compare PS/CO₃ ^2-/ MeOH and PS/CO₃ ^2-The UDMH of system is removed Rate, it can be seen that PS/CO₃ ^2-Methanol is relatively weak to the Inhibition of degradation of UDMH in/MeOH system, further demonstrates PS/CO₃ ^2- CO in system₃ ^·-Presence and its degradation facilitation to UDMH.

Based on above-mentioned confirmatory experiment, the degradation reaction mechanism of UDMH is as shown in fig. 6, in PS/CO₃ ^2-In system, peroxy-disulfuric acid Sodium firstly generates SO₄ ^·-, SO₄ ^·-Energy and OH under alkaline environment^-Reaction generate OH, both free radicals can in system CO₃ ^2-、HCO₃ ^-Reaction generates CO₃ ^·-、HCO₃ ^·, and then promote the degradation of UDMH.

3, comparative test: the UDMH solution that 100mL initial concentration is 100mg/L is added in 150mL conical flask, by not Quantitative sodium-chloride water solution is added with initial concentration and is placed on water-bath constant temperature oscillator, wait be preheating to 70 DEG C, by initial concentration Sodium persulfate is added for 20mmol/L to start to react, every 10min, takes 0.2mL sample to be put into colorimetric cylinder, is mentioned in colorimetric cylinder Before be put into ice water to terminate reaction, then carries out UDMH content measuring with spectrophotometry, calculating UDMH removal rate.

Various concentration Cl^-The influence that (5,10,50,100mmol/L) degrade to UDMH is as shown in fig. 7, although Cl^-It can be with SO₄ ^·-Reaction generates chlorine radical (Cl^·), Cl^·Itself is also oxidizing, but it can be seen from figure 7 that chloride ion presence pair UDMH degradation has faint inhibiting effect.

(4) influence of the sodium persulfate initial concentration to UDMH oxidative degradation

The UDMH solution that 100mL initial concentration is 100mg/L is added in 150mL conical flask, is by initial concentration 1mmol/L is added aqueous sodium carbonate and is placed on water-bath constant temperature oscillator, wait be preheating to 70 DEG C, is added by different initial concentrations Two sodium sulphate start to react, and every 10min, 0.2mL sample are taken to be put into colorimetric cylinder, ice water are put into colorimetric cylinder in advance to terminate Then reaction carries out UDMH content measuring with spectrophotometry, calculate UDMH removal rate.

As shown in figure 8, the removal rate of UDMH is constantly increased as sodium persulfate initial concentration increases, when PS is initially dense When degree is increased to 20mmol/L by 1mmol/L, removal rate of the UDMH in 60min is promoted by 51.1% to 95.8%.